基于聚氨基苯硼酸修饰电极的新型pH传感器

采用电聚合方法制备了聚氨基苯硼酸(PABA)膜修饰玻碳电极的新型pH传感器。利用红外图谱和交流阻抗谱对PABA膜的修饰进行了表征。考察了该修饰电极在不同pH的Britton-Robinson(BR)缓冲溶液中的循环伏安响应。结果表明,阴极还原峰电位与底液pH具有良好的线性关系,线性范围为pH 2.01~8.00,能斯特响应斜率为-153 mV/pH。将该修饰电极用于弱酸及中性实际样品pH测定,结果满意。     

基于Schiff-base结构化合物载体的汞离子选择性电极的制备与表征

高产率合成了一种新的Schiff-base结构化合物,并将其表征为高选择性聚合物膜汞离子选择性电极载体。考察了不同增塑剂及离子交换剂对膜电极响应性能的影响,在最佳膜组分条件下测得该电极对汞离子的线性响应范围为1.0×10-6~3.0×10-4mol/L,响应斜率为(29.3±0.3)mV/dec,检出限为2.6×10-7mol/L;该电极响应速率快(小于12 s),可在较宽的pH范围内(pH2.8~5.6)使用,且其它常见碱金属、碱土金属以及过渡金属离子对该测试电极的干扰小;可准确检测自来水中汞离子的浓度。     

锂离子选择性光电二极管传感装置的研究及在血清分析中的应用

将锂离子选择性中性载体和亲脂性pH指示剂结合在增塑的PVC膜中,pH缓冲液中锂离子浓度的变化将引起膜颜色的改变.将该膜涂覆在光电二极管光敏区并与发出锐线光的发光二极管组装在一起,构成了一种新型锂离子选择性传感装置.报道了这一传感装置的响应特性,探讨了临床分析应用的可能性.     

一种偶氮聚电解质在不同pH值条件下的静电逐层自组装研究

研究了一种光响应偶氮聚电解质(PEAPE)在不同pH值条件下的自组装,重点讨论了pH值对静电逐层自组装以及对光响应性能的影响.研究表明,在所研究的pH范围内,pH值越低,越有利于生成吸光度高的自组装膜,对应的自组装膜厚度也越大.红外光谱分析表明,偶氮聚电解质在不同pH溶液中存在不同的电离情况.pH值越低,用于自组装的溶液中的聚合物链上的电荷数越少,链构象越卷曲.解释了不同pH值条件下自组装膜吸光度和厚度差别的原因.     

聚苯胺/钴-氧化钴膜作传感元件的pH传感器的性能

研究了在玻碳电极上修饰不同物质所制得的pH传感器,通过电位滴定的方法比较得出先修饰聚苯胺,再修饰钴-氧化钴膜的电极对pH有较好的响应,能代替玻璃电极应用在实际样品测定中. 探究了最佳修饰条件为:先在0.1 mol/L苯胺的盐酸(1 mol/L)溶液中, 电位范围为-0.2～1.0 V,以100 mV/s 的扫描速率循环伏安扫描10圈修饰聚苯胺膜;接着在含2.0×10-4 mol/L Co2+的磷酸盐缓冲溶液(PBS)(pH=7.5)中,电位范围为-1.2～1.2 V,以100 mV/s的扫描速率循环伏安扫描 5圈修饰钴-氧化钴膜. 得到的修饰电极响应斜率为-61.60 mV/pH,响应范围pH值为0.5～13.     

适于测定苄胺的可逆光敏膜的研究

本文报道了一种测定苄胺的可逆光敏膜.将作为苄胺离子载体的联萘冠醚和亲脂的pH指示剂,结合在增塑的PVC膜中,苄胺离子与氢离子在膜相的竞争引起膜的吸光值变化.报道了该传感器的响应特性,推导了有关的理论关系式.     

左氧氟沙星选择性电极的制备及其性能研究

以左氧氟沙星与四苯硼酸根形成的缔合物为电活性物质,研制了一种左氧氟沙星PVC膜涂层玻璃电极,并对其响应性能进行了系统研究.实验表明,该电极的Nernst响应范围为5.0×10-3～2.0×10-5 moL/L,斜率为51.7 mV/pC,适用pH范围为3.0～4.5.该电极制作方法简单,响应迅速,重现性好,用于左氧氟沙星注射液和片剂的测定.     

丙烯酰胺反蛋白石凝胶膜的制备及pH响应性能研究

以聚苯乙烯(PS)胶体晶体为模板,采用"三明治"法得到收缩率较低、表面无覆盖层、三维长程有序的聚丙稀铣胺(PAM)反蛋白石凝胶膜。实验发现,粒径较小的模板有利于得到结构规整的凝胶膜。反蛋白石凝胶膜有明显的pH响应性,随着pH增大,PAM反蛋白石凝胶膜的最大衍射波长红移,且在pH=8.49时,达到最大;pH继续增大时,最大衍射波长表现为蓝移趋势。并且可重复响应而不破坏其结构,表明该凝胶膜具有较大的实用价值。     

电聚吡咯固定化酪氨酸酶电极的制备及性能

在应用恒电位法电化学聚合吡咯的同时 ,将酪氨酸酶固定在导电聚吡咯膜内 ,制成一种灵敏、稳定的酪氨酸电极 .讨论了溶液 pH值和聚合电位对酶固定化的影响 ,对酶分子嵌入吡咯膜前后的SEM图和CV曲线进行了分析、比较 .该电极对甲苯酚响应的线性范围为 5 .0× 10 -8～ 1.0× 10 -6mol/L ,最适 pH值为 6 .6 ,酶反应表观上遵循Michaelis_Menten动力学 ,表观米氏常数为 2 .2× 10 -5mol/L .     

基于荧光内滤效应的锂离子荧光化学传感器研究

报道了一种基于荧光内滤效应的荧光增强型锂离子光化学传感器,将荧光试剂、亲脂性pH指示剂和锂离子中性载体结合在增塑的PVC膜中,Li⁺与H⁺在膜相中的竞争萃取效应引起受亲脂性pH指示剂调制的敏感膜荧光值的变化.推导了有关理论关系式,研究了该传感器的响应特性,并对人工合成样品进行测试,结果较为满意.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.